Pad dyeing composition



Patented Feb. 3, 1953 PAD DYEI NG COMPOSITION Joseph M. Kuhn, Haddonfield, N. J., assignor to The Sherwin-Williams Ohio, a corporation of Ohio Company, Cleveland,

No Drawing. Application July 20, 1951, Serial No. 237,833

15 Claims.

This invention relates, as indicated, to an improved pad dyeing composition. More particularly, this invention relates to compositions which are particularly adaptable to pad dyeing for textiles having discrete fibers with insoluble pigments to produce a solid colored textile. In pad dyeing there is usually employed a bath comprising an emulsion of water and a volatile solvent, the latter containing the pigment and the resin binder or binders. One method of pad dyeing is to immerse the textile in the bath and then pass it between squeeze rolls which remove the excess of color and other bath constituents. As an alternate method, one of the squeeze rolls may be partially immersed in the color bath, whereby some of the bath is carried to the nip between the partially immersed roll and the roll adjacent to it. In this case the textile is dyed by passing between the rolls without previous immersion in the bath. A method of pad dyeing resin-bound water-insoluble pigments in a water emulsion has been disclosed by Jennings in Patent 2,344,199.

Although pigmented lacquer-in-water emulsions have been known and recommended for dyeing textiles, a serious drawback has been the difiiculty of preparing emulsions which will remain stable over a long period of time, and under those conditions which exist in the pad dyeing process where the textile and the emulsion are continuously squeezed between two or more tightly set squeeze rolls, this condition is more pronounced. Previous technique in the preparation of such textile coating compositions has specified the use of a volatile solvent for the resinous binder, which solvent has been either a water-soluble organic solvent or a water-insoluble organic solvent. The compositions of this invention are not properly designated as lacquer-in-water emulsion since there is nosubstantial amount of solvent for the resin present therein. Water is, however, the external phase, and resin, plasticizer and pigment (which is dispersed in the resin) constitutes the internal or discontinuous phase. For all practical purposes, these compositions are solvent-free as will be more clearly explained hereinafter and will be designated as resin-in-water emulsions.

It is a novel feature of my invention to provide pad dyeing compositions and a method of employing the same which compositions contain no volatile water-insoluble organic solvents for the resin, such as commonly employed heretofore, and relatively minor proportions, on the order of less than 1%, of volatile water-soluble organic solvents for the resin. In addition to the ordinary advantages obtained in eliminating a solvent from any system, namely, economy and avoidance of the usual hazards encountered when employing solvents, it has been found most unexpectedly that extremely fine dispersions are obtainable resulting in a uniform dyeing eliect when the material is padded, dried, and cured and improved fastness properties are obtained. For the purposes of this invention and the ensuing disclosure, volatile solvents are to be considered volatile when the boiling point at atmospheric pressure is less than 225 C.

The compositions of this invention differ materially from those heretofore employed in that no reliance is made upon the presence of volatile solvents to secure adequate penetration and even dyeing.

It is, therefore, a principal object of this invention to provide a substantially volatile solventfree pad dyeing composition.

Other objects of this invention will the description proceeds.

To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described and particularly pointed out in the appended claims, the following description setting forth in detail certain illustrative embodiments of the invention, such disclosed means constituting, however, but a few of the various forms in which the principle of this invention may be employed.

Broadly stated, therefore, this invention comprises the provision of a resin-water emulsion suitable for use in pad dyeing baths in which the resinuous binder comprises a water-insoluble cellulose ether, a water-insoluble alkylated melamine-aldehyde resin and a non-volatile plasticizer, said resinous binder having dispersed therein a water-insoluble pigment, and in which emulsion the aqueous phase compriseswater', said emulsion being free of water-insoluble organic solvents and containing less than 5% by weight of a water-soluble organic solvent. Film-iorm-. ing ingredients are to be considered, for the pur appear as posesof this invention, as including the melamine-aldehyde resin, the cellulose ether, the plasticizer and other such organic materials which remain on drying in the film. The term is exclusive of pigments and the aqueous phase.

The compositions of this invention are usually prepared in the form of a concentrate which is diluted with water by the ultimate user to a proper consistenc and depth of color for pad dyeing. Examples which are given below, provide concentrates. These concentrates are employed in' amounts ranging from 0.05% to about 5%, water constituting the balance, to provide a suitable pad dyeing bath. When so diluted, the compositions of this invention as padded will contain from about 0.01% to no more than 1% by weight of a volatile water-soluble organic solvent. Most generally, the amount of such solvent in the dye bath is no more than 0.25% by weight.

In the concentrated form, the amount of such solvent will be proportionately larger ranging from 0.05 to about 5%, more generally, 2.5% or less. The only reason any volatile water-soluble organic solvent is present at all in any of these,

compositions is to facilitate handling of the melamine-aldehyde resin in compounding operations. Such solvent serves no other useful purpose and is, therefore, unnecessary in the final compositions.

The alkylated melamine formaldehyde condensation products which are useful in accordance with this invention may be prepared by known methods. For example, reference may be had to the patent to Widmer, 2,197,357, and the patent to Swain, Re. 22,402. sation products are prepared by reacting 2 to 6 mols of formaldehyde with 1 mol of melamine. The condensation product formed is believed to be mostly methylol-melamine.

When preparing the various alkylated melamine formaldehyde condensation products, it is frequently desirable to prepare first the methylated methylo-l-melamine and then, by an interchange process utilizin an aliphatic alcohol of the desired carbon atom content, e. g., 3 to 12 carbon atoms, obtain the corresponding alkylated methylol-melamine. Specific examples of such treatment are also given in the patent to Johnstone et al., Re. 22,566.

Specific examples of the alkylated melamine formaldehyde condensation products which may be used in accordance with this invention include propylated methylol-melamine, butylated methyl'ol-melamine, hexylated methylol-melamine, cy-clohexylated methylol-melamine, caprylatecl methylol-melamine, lauryla ted methyl-ol-melamine, etc.

A preferred material for use in accordance with this invention is the butylated melamineformaldehyde product, primarily because of its ready availability on the market, and for this reason it has been used in the specific examples which follow at a later point in the specification, but which will be understood as merely illustrative of the use of other such alkylated methylol-melamines. The melamine-aldehyde resins containing less than 3 carbon atoms in the alkyl group tend to be too soluble in water for the purposes of this invention.

The water-insoluble cellulose ethers which have been found to be useful in accordance with this invention include aliphatic cellulose ethers, e. g., ethyl cellulose, propyl cellulose, butyl cellulose, benzyl cellulose, mixed ethyl benzyl cellu lose, mixed ethyl butyl cellulose, etc. In general,

In general, these condenthese ethers are sufficiently etherified to be insoluble in water. For example, ethyl cellulose, which is preferred, will have an ethoxy content within the range of from about 40% to about and preferably from about 47% to about 48.5%. Such a material is available on the market and has a viscosity of 10 centipoises. The a'lkyl cellulose ethers are a preferred class.

In general, the amount of melamine-formaldehyde resin is in excess of the amount of cellulose ether. It has been found that wash fastness is impaired if there be more than 1 part of cellulose ether to 1 part of resin by weight.

The emulsion as marketed may have a nonaqueous phase greater than 50 but when used for pad dyeing, it is greatly diluted with water.

It becomes convenient at this point to illustrate the manner of compounding the compositions of this invention by giving several specific examples which are to be understood as being illustrative of the principles of this invention and not for the purpose of limiting the invention to the precise compositions which are shown.

EXAMPLE I 1000 grams of Melmac 245-8 (a butylated melper phthalocyanine) containing 200 grams of pigment, and grams of a 50% aqueous solution of a sodium salt of a naphthalene sulphonic acidformaldehyde condensation product (Blancol) were mixed to yield a dispersion. To this mixture were then added 100 grams of butyl Cellosolve and 300 grams of the above resin-plasticizer mixture. The pigment was then flushed into the lacquer phase from the aqueous phase and. 970 grams of water, butyl Cellosolve and a dispersing agent were removed. The resulting composition was then washed three successive times with 800 gram portions of water following which there were removed 806 grams of water and butyl Cellosolve, 803 grams of water and butyl Cello solve and 826 grams of water and butyl Cellosolve, respectively. 200 grams of ethyl cellulose (10 centipoise standard ethoxy) were then added and the batch mixed to dissolve. An additional 500 grams of the above resin plasticized mixture were then added together with 104 grams of oleic acid, 52 grams of triethanolamine, 1500 grams of water and 15 grams of ammonia (27% NHs).

The pigmented resin plasticizer mixture was very well dispersed in water and found to remain stable on storage for periods of up to 2 to 3 years. This printing paste contains no waterinsoluble volatile organic solvents, the only volatile solvent employed being butyl Cellosolve which is completely soluble in water. The repeated washings with water effectively removed from the composition all but a very minor percentage of such solvent.

Dyeings made with the above color composition according to the usual pad dyeing technique showed excellent appearance and f-astness properties.

A mylated melamine-formaldehyde resin may be used in place of part or all of the butylated melamine-formaldehyde resin or this example.

EXAMPLE II In this example there was used a solvent-free solid form of butylated melamine-formaldehyde resin known as Resimene 888. The materials employed, with .brief indications as to the steps, are as follows:

1,466 gm. Monastral Blue press cake (300 gm.

pigment) 150 gm. Blancol solution 50% Mix to disperse 150 gm. butyl Cellosolve 240 gm. Resimene 888 Premix to dissolve 240 gm. dibutyl phthalate Flush and remove 1,273 gms. water and butyl Cellosolve. Add: 500 gm. water Wash and remove 534 gm. water 150 gm. ethyl cellulose cp. standard ethoxy) Mix until dissolved 166 gm. oleic acid 83 gm. monoethanolamine 1,425 gm. water 37 gm. ammonia (27% NHs) Butyl Cellosolve is a monobutyl ether of ethylene glycol. Other pigments may, of course, be employed.

EXAMPLE III The materials employed, with a brief indication as to the steps, .are as follows:

941 gm. Mona-stral Green press cake (250 gm.

pigment) gm. Blancol solution 50 gm. butyl Cellosolve gm. Resimene 888 gm. dibutyl phthalate Flush and remove 652 gm. water.

gm. water Wash and remove 534 gm. water gm. ethyl cellulose (10 cp. standard ethoxy) Mix to dissolve gm. oleic acid.

gm. triethanolamine gm. Water gm. ammonia (27% NH2) Premix to dissolve Add! EXAMPLE IV ifhe materials employed, with a brief indication as to the steps, are as follows:

1,129 gm. Monastral Green press cake (300 gm.

pigment) gm. Blancol solution 50 Mix to disperse gm. butyl Cellosolve gm. Resimene 888 gm. dibutyl phthalate Flush and remove 773 gm, water gm. water Wash and remove 513 gm. water gm. ethyl cellulose (10 op. standard ethoxy) Mix until dissolved gm. oleic acid gm. triethanolamine water gm. ammonia (27% NH3) Premix to dissolve 6 EXAMPLE v The materials employed, with a brief indication as to the steps, are as follows:

Resin solution 500 gm. Resimene 888 250 gm. butyl Cellosolve 250 gm. loutyl cellosolve Mix thoroughly until dissolved Padding color 454 gm. Monastral Blue pres-s cake (136 gm.

pigment) 68 gm. Blancol solution 50 217 gm. above resin solution Flush and remove 358 gm. water gm. ethyl cellulose (10 cp. standard ethoxy) Mix until dissolved. Add:

300 gm. water Wash and remove 253 gm. water. Add: 300 gm. water Wash and remove 286 gm. water. Add: 300 gm. water Wash and remove 305 gm. water gm. Pfiaumers ester P-153-S gm. Triton X- gm. ammonia (27% NH3) gm. water Ester P--l53-S, is a fatty acid ester of a mannitol or sorbitol type alcohol. Triton X-l00 is an ethylene oxide condensation product. Both are emulsifiers.

All the ethyl cellulose used in the following experiments is of the 10 cp., 46.8-48.5% ethoxy content type.

The following example employs the resin, ethyl cellulose, plasticizer, and water soluble solvents in a single solution.

EXAMPLE VI The materials employed, with a brief indication as to the steps, are as follows:

217 289 108 Premix and dissolve water 600 water 600 water 600 EXAMPLE VII The materials errlployedwith a brief indication as to the steps,are as follows:

ec ema 464 gm. Monastral Green press cake (140 gm. Pi me t V, 109 gm. Resimene 868 54 gm. dibutyl phthalate V g 54 gm. ethyl alcohol Flush and remove 313 gm. water 68 gm. ethyl' cellulose, t 50; gm. ethyl alcohol Mix until dissolved gm. water Wash and remove 300 gm. water gm. water Wash and remove 300 gm. water gm. Pflaumers ester P-153-S gm. Triton X-l gm. ammonia (27% NHa) gm. water Premix and dissolve EXAMPLE VIII The materials employed, with a brief indication as to the steps, are as follows:

464 gm. Monastral Blue press cake (140 gm.

pigment) gm. Resimene 888 gm. dibutyl phthalate gm. acetone Flush and remove 319 gm. water gm. ethyl cellulose cp. Mix to dissolve gm. water Wash and remove 300 gm. water 50 gm. Pflaumers ester P-l53-S 50 gm. Triton X-l00 25 gm. ammonia (27% NH?) 445 gm. water 54 Premix and dissolve This example starts with a pigment pres cake instead of a water dispersion, and uses a watersoluble volatile organic solvent other than butyl Cellosolve.

EXAMPLE IX The materials employed, with a brief indication as to the steps, are as follows:

464 gm. Monastral Green press cake (140 gm.

pigment) 109 gm. Resimene 888 54 g zg ig Premix and dissolve 54 gm. methyl Cellosolve Flush and remove 331 gm. water 68 gm. ethyl cellulose 10 cp.

Mix and dissolve 300 km. water Wash and remove 300 gm. water 300 gm. water Wash and remove 300 gm. water 50 gm. Pflaumers ester P-153-S 50 gm. Triton X-100 25 gm. ammonia (27% NH3) 457 gm. Water This example uses still another water soluble volatile organic solvent.

EXAMPLE X The materials employed, with a brief indication as to the steps, are as follows:

Premix and dissolve Uses an alcohol-type plasticizer.

EXAMPLE XI The materials employed, with a brief indication as to the steps, are as follows:

464 gm. Monastral Green press cake (140 gm.

pigment) 109 gm. Resimene 888 54 gm. blown castor oil 54 gm.butylCe1losolve Flush and remove 315 gm. water gm. ethyl cellulose 10 cp.

Mix until dissolved gm. water g Wash and remove 300 gm. water gm. water Wash and remove 300 gm. water gm. water Wash and remove 300 gm. water gm. Pflaumers ester P-153-S gm. Triton X- gm. ammonia (27% NHs) gm. water Premix and dissolve 2,215 gm. 7 Uses a natural oil-type plasticizer.

EXAMPLE XII The materials employed, with a brief indication as to the steps, are as follows:

109 gm. Resimene 888 54 gm. dibutyl phthalate 54 gm. butyl Cellosolve gm. Vulcan Red BA (General Dyestufi Corp.

Pat. No. 1,977,936) Mix and grind on roller mill, transfer to mixer. Add: 68 gm. ethyl cellulose 10 op. 50 gm. Triton X-100 20 gm. ammonia (27% NI-Is) 505 gm. water Premix and dissolve In this example a dry pigment was ground into the resin vehicle with a sufiicient loss of volatile, water-soluble, butyl Cellosolve so as not to interfere with the emulsification.

In the above examples there'have been made padding colors for dyeing textile fabrics by flushing or grinding water-insoluble pigments in a resin solution containing:

Alkylated melamine formaldehyde resin A non-volatile plasticizer A water-soluble volatile organic solvent, capable of dissolving the resin and ethyl cellulose, and largely removed during the compounding steps.

This solution may or may not include a cellulose ether.

After flushing or grinding, the ethyl cellulose, not included in the original solution is dissolved. If the color has been flushed from a water dispersion or presscake, a washing operation to remove most of the water-soluble volatile organic solvent is performed. In the cases where dry pigment is ground into the resin solution, this removal of volatile solvent is accomplished by evaporation. After the incorporation of a suitable amount of emulsifier, this mass is then capable of being dispersed in water by the slow addition of water.

The resulting product is a resin bound pigment dispersed in water containing no waterinsoluble volatile solvents, and only very small quantities of water-soluble solvents. The dispersion in water is so fine that penetration into the threads and around the fibres of a fabric is phases and be fast to light.

10 system for the purpose of facilitating the formation of a stable emulsion of the principal ingredients.

With respect to the pigments employed in these compositions, it is desirable that they be inert with respect to the balance of the compositions, insoluble in both the resin and the aqueous Resistance to dry cleaning fluids is also a desirable characteristic of these compositions, but for temporary displays, for example, the desirable characteristics of light fastness, washability, etc. are not essential. In the dyeing of textiles which are to have a. more permanent use, the pigments should be nonbleeding, light fast, and unaffected by cleaning solutions and soaps. Pigments suitable for use in this connection are well known and while an essential component of the compositions of this invention, they do not have a distinguishing class of characteristics other than insolubility in both of the phases of the completed emulsion.

For what may be a clearer presentation of the compositions of this invention, in the table below there have been tabulated the compositions of the preceding 12 examples in terms of parts per 1,000 parts of concentrated composition.

Table I Example No I II 111 IV V VI VII VIII IX x x1 XII Melamine-aldehyde lGSiIL. 136 86 as 112 100 80 100 100 100 100 100 100 0411111056 ether s 54 52 70 0s 5s 4s 0s 08 as as as Plasticizer 130 s0 83 112 54 44 54 54 54 54 54 54 Pigment as 107 104 140 136 112 140 140 140 140 140 140 Defiocculating agent 8 27 9 12 34 28 Water-solub1esolvent 30 41 4s 80 104 54 47 54 54 Emulsifying agent 54 03 61 105 87 107 107 107 107 107 55 Water 514 517 550 447 440 49s 43s 408 475 452 468 520 Total 1, 000 1,000 1,000 1,000 1,000 1,000 1,000 1,000 1,000 1,000 1,000 1,000

so complete that a uniform dyeing efiect is ob- 40 The foregoing table illustrates preferred contained when the textile is padded, dried, to remove the water, and cured.

Furthermore, superior fastness properties are obtained, when the fabric is dried and the resin polymerized, because the distribution of the resin and pigment is so even and the penetration so complete.

Unlike systems where water dispersions of pigments are added to resin latices, this system has superior fastness properties because the pigment is dispersed in the resin phase and is deposited I with it on the fabric, and not left to chance that a particle of pigment will find a particle of binder,

The plasticizers suitable for this process include any that are compatible with both ethyl cellulose and butylated melamine formaldehyde.

The water-soluble volatile solvents useful in rendering the melamine aldehyde resin more workable include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, acetone, diacetone alcohol, methyl Cellosolve (monomethyl ether of ethylene glycol), Cellosolve (monoethyl ether of ethylene glycol), isopropyl Cellosolve (monoisopropyl ether of ethylene glycol), butyl Cellosolve (rnonobutyl ether of ethylene glycol), methyl acetate.

The Blancol solution used in the foregoing examples is a defiocculating agent for the presscake, and any other suitable deflocculating agent such as the sodium lignosulfonates may also be employed for this purpose. It should be noted that in certain instances such deflocculating agents are not required. The fatty acid, hydroxyl amine and ammonia appearing in certain of the foregoing examples is an emulsification agent centrations of the various components in the preferred compositions illustrated by Examples I through XII. Such ingredients may have the following preferred ranges of concentration for most satisfactory results:

Melamine-aldehyde resinfrom about 8 to about 11 parts/ 1 Cellulose ether-from about 4.5 to about 7 parts/100 Plasticizer-from about 4 to about 17 parts/100 Pigmentfrom about 7 to about 14 parts/100 Defiocculating agent-from 0 to about 3.5

parts/ 100 Water-soluble solventfrom about .5 to about 10.4 parts/100 Emulsifying agentfrom about 5 to about 11 parts/100 Water-fr0m about 43 to about 54 parts/100 These are to be construed as preferred ranges from which variations may be made without departing from the spirit of this invention. With respect to the water-soluble solvent, however, it should be pointed out that these figures are somewhat misleading and, in all probability, somewhat high in value since during many of these operations, these low boiling Water-soluble organic solvents are lost by evaporation to a much larger degree than is represented in the table above. Analysis has shown that in most cases the Watersoluble solvent content in the concentrated materials rarely exceeds 5% by weight. The figures in the foregoing table are calculated by weight balance from the preceding specific examples, in which calculations no allowance has been made for evaporation of the solvent during the formusition.

lating process. As indicated above, however, final analysis of the concentrated compositions has shown that in general, the amount of such solvent is less .than.5% byweight of the entire compo- It should also be borne in mind that thesecon- 'centrates are used in making a pad dyeing bath in which baths the concentration of the concen- "trates never exceeds about by weight, and 1 generally is used at a concentration of about 2.5%.. Smaller amounts of the concentrate may be used. Since no more than about 10% of this pigmented emulsion would be'included in a' dye bath for application onto textile materials, the

amount of volatile solvents in the dye bathwould be 1% or less and for the purposes of this invention a maximum amount of 1% of such watersoluble'organic solvents is to be construed as substantially no solvent appearing in the final pad dyeing bath. Water may be added to the. concentrates of this invention to eifect the desired reduction to pad dyeing bath concentration, the amount of Water so added being generally in the range of from about 90 to about 99 parts per 100 parts of finished pad dyeing bath, and preferably from about 95 to about 97.5 parts of water per 100 parts of bath, the balance being a concentrate suchas exemplified above.

Other modes of applying the principle of this .invention may be employed instead of those specifically set forth above, changes being made as regards the details herein disclosed, provided the elements set forth in any of the following claims, or the equivalent of such be employed.

I, therefore, particularly point out and distinctly claim as my invention:

1. A resin-in-water emulsion suitable for use in pad dyeing baths in which the resinous binder comprises a water-insoluble cellulose ether, a water-insoluble alkylated melamine-aldehyde resin and a non-volatile plasticizer, said resinous binder having dispersed therein an insoluble pigment, and in which emulsion the aqueous phase comprises water, said emulsion being free of water-insoluble organic solvents and containing less -than5% by weight of a water-soluble organic solvent.

2; -A pad dyeing composition of the resin-in- Water emulsion type in which the resinous binder comprises a water-insoluble cellulose ether, a water-insoluble alkylated melamine-formaldehyde'resi'n and a non-volatile plasticizer, said resinous binder having dispersed therein an insolublepigmentand in which the aqueous phase comprises water, said composition containing no water-insoluble volatile organic solvent and less than 1 by weight of a water-soluble volatile organic solvent.

3. A resin-in-water emulsion suitable for use in pad dyeing baths in which the resinous binder comprises a water-insoluble cellulose ether, a water-insoluble alcohol modified methylated .methylol-melamine and a non-volatile plasticizer,

said resinous binder having dispersed therein an insoluble pigment, and in which emulsion the aqueous phase comprises water, said emulsion be- .ing free of water-insoluble organic solvents and containing less than 5% by Weight of a watersoluble organic solvent.

4. A composition in accordance with claim 1 in which the alkylated melamine-aldehyde resin is which the alkylated melamine-aldehyde resin is a r 12 V. melamine-formaldehyde resin modified with butyl alcohol.

6. A composition in accordance with claim 1 in which the cellulose ether is an aliphatic cellulose ether.

7. A composition in accordance with claim 1 in which the cellulose ether is an alkyl cellulose ether.

8. A composition in accordance with claim I in which the cellulose ether is ethyl cellulose having an ethoxy content'within the range of from about 40% to about 50%.

9. A composition in accordance with claim 1 in which the amount of cellulose ether by weight is no more than the amount of alkylated melamine-aldehyde resin by weight.

10. A resin-in-water emulsion suitable for use in pad dyeing baths in which the resinous binder comprises a water-insoluble ethyl cellulose having an ethoxy content within the range of from about 40% to about 50%, a water-insoluble butylated melamine-formaldehyderesin and a nonvolatile plasticizer, said resinous binder having dispersed therein an insoluble. pigment, and in which emulsion the aqueous phase comprises water, said emulsion being free of water-insoluble organic solvents and containing less than 5% by which composition, theratio of ethyl cellulose to butylated melamine-formaldehyde resin is no more than 1 part of resin by weight. v

11. The method of pad dyein to produce a solid color effect which comprises subjecting textile materials having discrete fibers to a resin-inwater emulsion in which the resinous binder comprises a water-insoluble cellulose ether, a waterinsoluble alkylated melamine-aldehyde resin and a non-volatile plasticizer, said resinous binder having dispersed therein an insoluble pigment, and in which emulsion,.the aqueous phase comprises Water, said emulsion being free of waterinsoluble organic solvents and containing less than 1 by weight of a water-soluble organic solvent, and then drying the material to remove the water.

12. The product produced by the method of claim 11.

13. A pad dyeing bath for textiles comprising a water reduction of the following composition, the amount of Water used for said reduction being from about to about 99 parts per 100 parts of pad dyeing bath:

Melamine-aldehyde resin-from about 8 to about 11 parts per 100 parts concentrate;

Water-insoluble cellulose-ether-from about 4.5

to about 7 parts per 100 parts concentrate;

Non-volatile plasticizer-from about 4 to about 1''! parts per 100 parts concentrate;

Deflocculating agentup to about 3.5 parts per 100 parts concentrate;

Organic water-soluble solvent-from about 0.5 to about 10.4 parts per 100 parts concentrate; Emulsifying agent-from about 5 to about 11 parts per 100 parts concentrate; Water-from about 43 to about 54 parts per 100 parts concentrate.

ethyl cellulose to 1 part of 14. The method of pad dyeing to produce a solid color effect which comprises subjecting textile materials having discrete fibers to a resin-inwater emulsion in which the resinous binder comprises a water-insoluble ethyl cellulose having an ethoxy content within the range of from about 40% to about 50%, a water-insoluble butylated 13 14 melamine formaldehyde resin and a non-volatile 15. The product produced by the method of plasticizer, said resinous binder having dispersed claim 14. therein an insoluble pigment, and in which the JOSEPH M. KUHN. aqueous phase comprises water, said emulsion being free of water-insoluble organic solvents and 5 REFERENCES CITED containing less than by Weight of a Water The following references are of record in the soluble organic solvent, and in which composim f this t tion the ratio of ethyl cellulose to butylated melamine formaldehyde resin is no more than 1 part UNITED STATES PATENTS of ethyl cellulose to 1 part of resin by Weight, and 10 Number Name Date then drying the material to remove the water. 2,527,530 Cassel Oct. 31, 1950 

1. A RESIN-IN-WATER EMULSION SUITABLE FOR USE IN PAD DYEING BATHS IN WHICH THE RESINOUS BINDER COMPRISES A WATER-INSOLUBLE CELLULOSE ETHER, A WATER-INSOLUBLE ALKYLATED MELAMINE-ALDEHYDE RESIN AND A NON-VOLATILE PLASTICIZER, SAID RESINOUS BINDER HAVING DISPERSED THEREIN AN INSOLUBLE PIGMENT, AND IN WHICH EMULSION THE AQUEOUS PHASE COMPRISES WATER, SAID EMULSION BEING FREE OF WATER-INSOLUBLE ORGANIC SOLVENTS AND CONTAINING LESS THAN 5% BY WEIGHT OF A WATER-SOLUBLE ORGANIC SOLVENT. 